U.S. patent number 4,645,805 [Application Number 06/711,291] was granted by the patent office on 1987-02-24 for adhesive composition and adhesive film or sheet on which the composition is coated.
This patent grant is currently assigned to Mitsubishi Gas Chemical Company, Inc.. Invention is credited to Morio Gaku, Nobuyuki Ikeguchi, Hidenori Kimbara.
United States Patent |
4,645,805 |
Gaku , et al. |
February 24, 1987 |
Adhesive composition and adhesive film or sheet on which the
composition is coated
Abstract
An adhesive composition comprising at least (A) at least one
cyanate ester compound selected from the group consisting of: (i)
polyfunctional aromatic cyanate ester monomers having the formula
wherein n is integer of 2-10 and R is an aromatic organic group,
the cyanate groups being bonded to an aromatic ring or said
aromatic organic group; (ii) homoprepolymers of (i) and (iii)
coprepolymer of (i) and an amine, and (B) at least one
thermoplastic saturated polyester resin which is non-crystalline,
substantially non-crystalline or of low crystallinity is disclosed.
The adhesive composition has excellent heat resistance, moisture
resistance and chemical resistance.
Inventors: |
Gaku; Morio (Saitama,
JP), Ikeguchi; Nobuyuki (Ibaraki, JP),
Kimbara; Hidenori (Tokyo, JP) |
Assignee: |
Mitsubishi Gas Chemical Company,
Inc. (Tokyo, JP)
|
Family
ID: |
26388731 |
Appl.
No.: |
06/711,291 |
Filed: |
March 13, 1985 |
Foreign Application Priority Data
|
|
|
|
|
Mar 14, 1984 [JP] |
|
|
59-48459 |
May 7, 1984 [JP] |
|
|
59-90697 |
|
Current U.S.
Class: |
525/437; 524/539;
525/175; 525/177; 525/176; 528/288 |
Current CPC
Class: |
C09J
167/00 (20130101); C09J 7/10 (20180101); C09J
167/00 (20130101); Y10T 428/14 (20150115); C08L
2666/02 (20130101); C08L 2666/02 (20130101) |
Current International
Class: |
C09J
167/00 (20060101); C09J 7/00 (20060101); C08L
067/02 () |
Field of
Search: |
;525/437 ;528/288 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Bleutge; John C.
Assistant Examiner: Short; Patricia
Attorney, Agent or Firm: Browdy and Neimark
Claims
What is claimed is:
1. An adhesive composition consisting essentially of:
(A) at least one cyanate ester compound selected from the group
consisting of:
(i) polyfunctional aromatic cyanate ester monomers having the
formula
wherein n is an integer of 2-10 and R is an aromatic organic group,
the cyanate groups being bonded to an aromatic ring or said
aromatic organic group;
(ii) homoprepolymers of (i) and
(iii) coprepolymer of (i) and an amine, wherein the composition
contains
(B) at least one essentially amorphous thermoplastic saturated
polyester resin, said saturated polyester resin consisting
essentially of a condensate of an aromatic or aliphatic
dicarboxylic acid of the formula ##STR4## wherein R is an aromatic
or aliphatic hydrocarbon radical or an acid anhydride of said
aromatic or aliphatic dicarboxylic acid, and an aliphatic or
alicyclic polyol.
2. The composition of claim 1 wherein the composition further
contains (C) at least one thermoplastic resin other than (B),
inorganic filler or mixture thereof.
3. The composition of claim 1 wherein number average molecular
weight of the polyester resin (B) calculated from terminal
functional groups is in the range of 5,000-22,000.
4. The composition of claim 1 wherein hydroxyl value of the
polyester (B) is in the range of 1-30 mg KOH/gram.
5. The composition of claim 1 wherein said polyester resin (B) is
employed in amount of 1-60% by weight on the basis of the total
weight of components (A) and (B).
6. The composition of claim 1, wherein said aromatic or aliphatic
dicarboxylic acid or said acid anhydride of said aromatic or
aliphatic dicarboxylic acid is selected from the group consisting
of terephthalic acid, isophthalic acid, malonic acid, succinic
acid, adipic acid, pimeric acid, suberic acid, azelaic acid,
sebacic acid and lower alkyl esters, acid anhydrides of said acids,
thermal decomposition products of carboxyl-terminated saturated
polyester resins, and mixtures thereof, and said aliphatic or
alicyclic polyol is selected from the group consisting of ethylene
glycol, propylene glycol, 1,3-propanediol, 4,1-butanediol,
1,5-pentanediol, 1,6hexanediol, neopentylglycol, diethylene glycol,
triethylene glycol, polyethylene glycol, polypropylene glycol,
polybutylene glycol, polycaprolactone diol,
2,2-dimethylpropanediol, 2,2-bis(4- hydroxy-cyclohexyl)propane,
1,4-dihydroxymethyl cyclohexane, trimethylol propane,
1,2,3-trihydroxypropane, tetramethylol methane, and mixtures
thereof.
7. An adhesive sheet comprising a release film or sheet and the
composition of claim 1 coated on the film or sheet.
Description
BACKGROUND OF THE INVENTION
This invention relates to a novel adhesive composition and an
adhesive sheet on which the composition is coated. The adhesive
composition and the adhesive sheet have excellent heat resistance,
moisture resistance, chemical resistance, flexibility, workability,
molding property and storage stability.
U.S. Pat. No. 4,110,364 discloses curable resin compositions
comprising a cyanate ester compound, and a polyfunctional
maleimide, and optionally an epoxy resin or other thermosetting
resin monomer or prepolymer. U.S. Pat. No. 3,562,214 discloses
curable resin compositions comprising a cyanate ester compound and
an epoxy resin.
Incorporation of butadiene-acrylonitrile compolymer into the above
polyvinyl acetate into the above compositions (Japanese Patent
Publication (kokoku) No. 40179/1982), incorporation of dimer
acid-based polyamide into the above compositions, (Japanese Patent
Publication (kokai) No. 206673/1983), incorporation of
1,2-polybutadiene rubber into the above compositions (U.S. Pat. No.
4,404,330) and incorporation of acryl rubber into the above
compositions (U.S. Pat. No. 4,396,745) were also known.
The resin composition into which butadiene-acrylonitrile copolymer,
polyvinyl acetate, or dimer acid-based polymer is incorporated have
somewhat poor adhering property and moisture resistance in normal
state. The resin composition into which thermoplastic polyurethane
is incorporated has somewhat poor moisture resistance, and
compatibility of the polyurethane to the resin composition is
insufficient, and long time storage stability of the composition is
bad.
On the other hand adhesive compositions comprising polyester resin
itself which is either non-crystalline or of low crystallinity,
(i.e., essentially amorphous), or adhesive compositions comprising
the polyester and epoxy resin were known. Although these
composition have excellent adhering property and flexibility, they
are poor in respect of heat resistance, bonding force at elevated
temperature and hardness.
SUMMARY OF THE INVENTION
We found that a resin composition comprising a cyanate ester
compound and a thermoplastic, saturated polyester resin, which is
either non-crystalline or of low crystallinity (i.e., essentially
amorphous), and optionally a polyfunctional maleimide, epoxy resin
or other thermosetting resin monomers or prepolymers and other
thermoplastic resin has excellent heat resistance, moisture
resistance, chemical resistance, electrical properties,
flexibility, resistance to general purpose organic solvents, such
as acetone, methyl ethyl ketone toluene and the like and storage
stability.
This invention relates to an adhesive composition comprising:
(A) At least one cyanate ester compound selected from the group
consisting of:
(i) polyfunctional aromatic cyanate ester monomers having the
formula
wherein n is integer of 2-10 and R is an aromatic organic group,
the cyanate groups being bonded to an aromatic ring or said
aromatic organic group,
(ii) homoprepolymers of (i) and
(iii) coprepolymer of (i) and an amine, and optionally (D) at least
one thermosetting resin monomer or prepolymer, characterized in
that the composition contains
(B) at least one thermoplastic, saturated polyester resin which is
non-crystalline, substantially non-crystalline or of low
crystallinity.
The invention also relates to an adhesive sheet comprises a release
film or sheet and the above composition coated on the film or
sheet.
DETAILED DESCRIPTION OF THE INVENTION
By "polyfunctional cyanate ester (A)" is meant a compound having at
least two cyanate groups in its molecule. The polyfunctional
cyanate ester is represented by the formula
wherein R is an aromatic nucleus-containing residue having 1-10
benzene rings selected from the group consisting of a residue
derived from an aromatic hydrocarbon selected from the group
consisting of benzene, biphenyl and naphthalene, a residue derived
from a compound in which at least two benzene rings are bonded to
each other by a bridging member selected from the group consisting
of ##STR1## wherein R.sub.2 and R.sub.3 are the same or different
and each represents a hydrogen atom or an alkyl group containing 1
to 4 carbon atoms, --O--, --CH.sub.2 OCH.sub.2 --, --S--, said
aromatic nucleus is optionally substituted by a substituent
selected from the group consisting of alkyl groups containing 1 to
4 carbon atoms, alkoxy groups, containing 1 to 4 carbon atoms,
chlorine and bromine; n is in an integer of at least 2 and
preferably 2-10, and the cyanate group is always directly bonded to
the aromatic nucleus.
Examples of the polyfunctional cyanate ester include 1,3- or
1,4-dicyanatobenzene; 1,3,5-tricyanatobenzene; 1,3-, 1,4-, 1,6-,
1,8-, 2,6- or 2,7-dicyanatonaphthalene;
1,3,6-tricyanatonaphthalene; 4,4'-dicyanatobiphenyl;
bis(4-cyanatophenyl)methane; 2,2-bis(4-cyanatophenyl)propane,
2,2-bis(3,5-dichloro-4-cyanatophenyl)propane,
2,2-bis(3,5-dibromo-4-cyanatophenyl)propane;
bis(4-cyanatophenyl)ether; bis(4-cyanatophenyl)thioether;
bis(4-cyanatophenyl)sulfone; tris(4-cyanatophenyl)phosphite;
tris(4-cyanatophenyl)phosphate;
bis(3-chloro-4-cyanatophenyl)methane; cyanated novolak derived from
novolak (U.S. Pat. Nos. 4,022,755; 3,448,079 etc.); cyanated
bisphenol type polycarbonate oligomer derived from bisphenol type
polycarbonate oligomer (U.S. Pat. No. 4,026,913) and mixture
thereof. Other cyanate esters employed in the practice of this
invention are given in U.S. Pat. Nos. 3,553,244; 3,755,402;
3,740,348, 3,595,900; 3,694,410 and 4,116,946 and BP Nos. 1,305,967
and 1,060,933 which are incorporated herein by reference. Of these
cyanate esters, divalent cyanate ester compounds which are derived
from divalent phenols, have symmetric structure and do not have any
condensed ring in their bridging portion, such as, for example,
2,2-bis(4-hydroxyphenyl)propane, are preferable, because they are
commercially available and give cured product having excellent
properties. Polycyanate compounds obtained by reacting a
phenol-formaldehyde precondensate with a halogenated cyanide are
also satisfactory. The above-mentioned cyanate esters may be used
as mixtures.
Prepolymers may be used containing a sym-triazine ring which is
prepared by the trimerization of the cyanate groups of the cyanate
ester, and which have a number average molecular weight of 300 to
6,000. Such prepolymers can be prepared by polymerizaing the above
cyanate esters in the presence or absence of, as a catalyst, an
acid such as a mineral acid or Lewis acid, a base such as sodium
hydroxide, a sodium alcoholate or a tertiary amine, a salt such as
sodium carbonate or lithirium chloride, or phosphate esters, such
as tributyl phosphine.
The polyfunctional cyanate ester can be used in the form of a
mixture of the monomer and the prepolymer. For example, many of the
commercially available cyanate esters derived from bisphenol A and
cyanogen halide are in the form of mixtures of cyanate monomers and
prepolymers, and such materials can also be used in the present
invention.
Polyfunctional maleimide compounds which can be employed as one of
component (D) have at least 2 maleimide groups in the molecule and
are represented by the following general formula ##STR2## wherein
R.sub.1 represents an aromatic or aliphatic organic group having a
valence of k, X.sub.1 and X.sub.2 are the same or different and are
independently a hydrogen atom, halogen atom or lower alkyl group
and k is an integer of at least 2 and preferably an integer of
2-10. Oligomers or prepolymers derived from the above maleimide
compounds may be used as the maleimide compound. Polyvalent,
aromatic or aliphatic organic groups represented by R.sub.1 in
formula (i) include the following:
(i) aliphatic or alicyclic hydrocarbon groups having 4-16 carbon
atoms,
(ii) polyvalent groups derived from aromatic hydrocarbons having
benzene or naphthalene ring, such as benzene, xylene or
naphthalene,
(iii) polyvalent groups derived from compounds in which at least 2
benzene rings are directly bonded, such as biphenyl,
(iv) aromatic ring-containing groups resulting from bonding of a
plurality of benzene rings either directly or through a bridging
member, represented by the formula ##STR3## wherein Y represents a
linear, branched or cyclic aliphatic hydrocarbon group having 1 to
14 carbon atoms, aromatic hydrocarbon group, such as a phenylene
group, a xylylene group, an oxygen atom, a sulfur atom, a carbonyl
group, a sulfonyl group, a sulfinyl group, an alkyleneoxyalkylene
group, a phosphonyl group, a phosphinyl group or an imino
group,
(v) melamine residues, and
(vi) residues of polynuclear product of benzene obtained by
reacting aniline with formaldehyde, generally residues of
polynuclear product having 2-10 benzene rings.
The maleimides represented by the above formula (i) can be produced
by a method known per se which involves reacting maleic anhydride
with divalent or more polyamine having at least 2 amino groups to
form a maleamide acid, and then dehydro-cyclizing the maleamide
acid. The maleimide can be produced by known methods per se.
Examples of polyfunctional maleimide include 1,3- or
1,4-dimaleimide benzene, 1,3- or 1,4-bis(maleimido methylene)
benzene, 1,3- or 1,4-dimaleimido cyclohexane, 1,3- or
1,4-bis(maleimidomethylene)cyclohexane, 4,4-dimaleimido biphenyl,
bis(4-maleimidophenyl)methane, bis(4-maleimidophenyl)ether,
bis(4-maleimidophenyl)sulfone, bis(4-maleimido-3-methylphenyl)
methane, bis(4-maleimido-3-chlorophenyl)methane,
bis(4-maleimido-3,5-dimethylphenyl)methane,
2,2-bis(4-maleimido-3-methylphenyl)propane,
2,2-bis(4-maleimido-3,5-dibromophenyl) propane,
bis(4-maleimidophenyl)phenylmethane,
3,4-dimaleimido-phenyl-4'maleimidophenylmethane,
1,1-bis(4-maleimidophenyl)-1-phenyl-methane, maleimide derived from
melamine and maleimide derived from addition product of
formaldehyde and an aniline in which two or more benzene rings bond
through methylene group.
The diamines include aromatic diamines, alicyclic diamines
aliphatic diamines. Aromatic diamines are preferable, because the
resulting object product have excellent heat resistance. When an
alicyclic diamine is used the object products having flexibility.
Primary diamines are more preferable to secondary diamines.
Examples of the amines include meta- or para-phenylenediamine,
meta- or para-xylylenediamine, 1,4- or 1,3-cyclohexanediamine,
hexahydroxylylenediamine, 4,4'-diaminobiphenyl,
bis(4-aminophenyl)methane, bis(4-aminophenyl)ether,
bis(4-aminophenyl)sulfone, bis(4-amino-3-methylphenyl)methane,
bis(4-chloro-4-aminophenyl)methane,
bis(4-amino-3,5-dimethylphenyl)methane,
bis(4-aminophenyl)cyclohexane, 2,2bis(4-aminophenyl)propane,
2,2-bis(4-amino-3-methylphenyl) propane,
2,2-bis(3,5-dibromo-4-aminophenyl)propane,
bis(4-aminophenyl)phenylmethane,
3,4-diaminophenyl-4'-aminophenylmethane and
1,1-bis(4-aminophenyl)-1-phenylethane, bis(4-aminophenyl)diphenyl
silane, bis(4-aminophenyl)methyl phosphoneoxide,
bis(4-aminophenyl)methyl phosphoneoxide, bis(4-aminophenyl)phenyl
phosphineoxide,
2,4-diamino-6-phenyl-1,3,5-triazine(benzoguanamine),
methylguanamine and butylguanamine.
Epoxy resins which can be used as one of component (D) are given in
U.S. Pat. Nos. 3,562,214 and 4,110,364 which are incorporated
herein by reference.
Examples of the epoxy resins include bisphenol A type epoxy resin,
bisphenol F type epoxy resin, phenol novolak type epoxy resin,
cresol novolak type epoxy resin, halogenated bisphenol A type epoxy
resin, halogenated phenol novolak type epoxy resin, alicyclic epoxy
resin, hydrogenated bisphenol A diglycidyl ether, triglycidyl
isocyanurate, tetraglycidyl -4,4'-diaminophenyl methane,
triglycicyl ether of tris(hydroxyphenyl) and the like.
In general, compound (D) may be added in amount of less than 60% on
the total weight of components (A) and (D).
The thermoplastic saturated polyester resins (B) which are
non-crystalline, substantially non-crystalline or of low
crystallinity may be condensate of an aromatic or aliphatic
dicarboxylic acid and an aliphatic or alicyclic polyol or
prepolymer thereof.
The number average molecular weight of the polyester calculated on
the basis of terminal functional groups of the polyester resin may
be in the range of from 1,500 to 25,000 and preferably from 5,000
to 22,000. The polyester with the number average molecular weight
of the above range are compatible with component (A). The hydroxy
value of the polyester resin may be in the range of from 1 to 30 mg
KOH/g. If the polyester resin has excess amount of free hydroxy
group or carboxyl group, the hydroxyl group or carboxyl group
reacts with the cyanate group of (A) gradually. As a result, the
resin composition can not be stored for a long time.
Examples of the dicarboxylic acids constituting the polyester resin
include terephthalic acid, isophthalic acid, malonic acid, succinic
acid, adipic acid, pimeric acid, suberic acid, azelaic acid,
sebacic acid, and lower alkyl esters, or acid anhydrides of these
acids and thermal decomposition products of carboxyl-terminated
saturated polyester resins.
Examples of the polyols or prepolymer of the diols constituting the
polyester resin include ethylene glycol, propylene glycol,
1,3-propanediol, 1,4-butenediol, 1,5-pentanediol, 1,6-hexanediol,
neopentylglycol, diethylene glycol, triethylene glycol,
polyethylene glycol, polypropylene glycol, polybutylene glycol,
polycaprolactone diol, 2,2-dimethylpropanediol,
2,2-bis(4-hydroxycyclohexyl)propane, 1,4-dihydroxymethyl
cyclohexane, trimethylol propane, 1,2,3-trihydroxypropane,
tetramethylol methane, and the like.
The polyesters obtained by reacting one of dicarboxylic acids with
one of polyols are necessarily crystalline. In order to obtain
polyesters which are non-crystalline, substantially non-crystalline
or of low crystallinity, combination of two or more dicarboxylic
acids and one or more polyol, or combination of one or more
dicarboxylic and two polyols are necessary. In general, polyesters
having repeating units of homogeneous monomers are crystalline.
When small amount of monomer having different structure is allowed
to exist into repeating units of homogeneous monomers, some of the
resulting polyesters is non-crystalline. Processes for producing
polyesters which are non-crystalline, substantially non-crystalline
or of low crystallinity are well known to those skilled in the
art.
Polyesters which are non-crystalline or substantially
non-crystalline (i.e., essentially amorphous) are preferable in the
practice of the present invention.
Polyester which is commercially available from Nippon Synthetic
Chemical Industry under name of POLYESTER is usable in the present
invention.
The proportion of component (A) to component (B) is not critical.
In general, the ratio of (A) to (B) may be in the range of from
10:90 to 99:1, more preferably 40:60 to 99:1 and most preferably
from 50:50 to 95:5. In case of coating the resin composition on a
release film or sheet it is preferable that component (B) is used
in amount of from 15 to 40% by weight.
Method of mixing component (A) and component (B) or components (A)
and (D), and component (B) is not critical. In general, solution of
(A) or (A) and (D) in an organic solvent is prepared, and then to
the solution is added (B) or solution of (B). Alternatively, (A),
or (A) and (D) free from a solvent and (B) free from a solvent may
be mixed in fusing state. An organic solvent or a reactive diluent
may be added to the mixture of (A) and (B), or (A), (D) and (B)
free from a solvent. Preliminary reaction of the mixture of (A) and
(B), or (A) (D) and (B) may be effected. The resin compositions in
solution, liquid or paste can be prepared.
The resin composition of this invention may be coated on a release
film or sheet. The resin-coated film or sheet may be dried at
100.degree.-150.degree. C. for 2 minutes-1 hour until uncured resin
free from a solvent or B-stage prepolymer can be obtained.
Examples of the release films or sheets include release paper,
fluoroethylene propylene film, and the like.
Reticulation of the curable resin composition produced according to
this invention may occur by heating.
A curable resin composition of the present invention may contain a
catalyst or catalysts in amount of several percent for the purpose
of accelerating reticulation.
Examples of the catalysts include imidazoles, such as
2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole,
2-phenylimidazole, 2-ethyl-4-methylimidazole,
1-benzyl-2-methylimidazole, 1-propyl-2-methylimidazole,
1-cyanoethyl-2-methylimidazole,
1-cyanoethyl-2-ethyl-4-methylimidazole,
1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole,
1-guanaminoethyl-2-methylimidazole and addition product of an
imidazole and trimellitic acid; tertiary amines, such as
N,N-dimethyl benzylamine, N,N-dimethylaniline,
N,N-dimethyltoluidine, N,N-dimethyl-p-anisidine,
p-halogene-N,N-dimethylaniline, 2-N-ethylanilino ethanol,
tri-n-butylamine, pyridine, quinoline, N-methylvorpholine,
triethanolamine, triethylenediamine,
N,N,N',N'-tetramethylbutanediamine, N-methylpiperidine; phenols,
such as phenol, cresol, xylenol, resorcine, and phloroglusin;
organic metal salts, such as lead naphthanate, lead stearate, zinc
naphthanate, zinc octoate, tin oleate, dibutyl tin maleate,
manganese naphthenate, cobalt naphthenate, and acetyl acetone iron;
and inorganic metal salts, such as stannic chloride, zinc chloride
and aluminum chloride; peroxides, such as benzoyl peroxide, lauroyl
peroxide, octanoyl peroxide, acetyl peroxide, para-chlorobenzyol
peroxide and di-t-butyl diperphthalate; acid anhydrides, such as
maleic anhydride, phthalic anhydride, lauric anhydride,
pyromellitic anhydride, trimetllitic anhydride, hexahydrophthalic
anhydride, hexahydropyromellitic anhydride and hexahydrotrimellitic
anhydride; azo compounds, such as azoisobutylonitrile,
2-2'-azobispropane, m,m'-azoxystyrene, hydrozones, and mixtures
thereof.
A variey of the additives, reinforcing agents and fillers can be
added to the curable resin as component (C) as long as they do not
impair the nature of the curable resin or the cured product.
Examples of these additives include natural resins, such as rosin,
shellac, copal, oil-modified rosin and the like; acrylate or
methacrylate esters or prepolymers thereof, such as esters of a
monofunctional or polyfunctional hydroxy compound and acrylic
methacrylic acid and alkenyl esters of acrylic or methacrylic
acids; polyallyl compounds or prepolymers thereof, such as diallyl
phthalate, divinyl benzene and trialkenyl isocyanurate;
dicyclopentadiene or prepolymer thereof; phenol resins; polyvinyl
acetal resins, such as polyvinyl formal, polyvinyl acetal and
polyvinyl butyral; phenoxy resins; acrylic resins having OH group
or COOH group; silicone resins; alkyl resins; petroleum resins; low
molecular liquid-high molecular elastic rubbers, such as
polybutadiene, butadiene-acrylonitrile copolymer, polychloroprene,
butadiene-styrene copolymer, polyisoprene, butyl rubber and natural
rubbers; vinyl polymers, such as polyethylene, polypropylene,
polybutene, poly-4-methylpentene-1, polyvinyl chloride,
polyvinylidene chloride, polystyrene, polyvinyl toluene, polyvinyl
phenol, AS resin, ABS resin, MBS resin, poly-4-fluorinated
ethylene, fluorinated ethylenepropylene copolymer,
tetrafluoroethylene-herafluoroethylene copolymer, polyfluorinated
vinylidene; resins, such as polycarbonate, polyester carbonate,
polyphenylene ether polysulfone, polyether sulfone, polyamide,
polyadomide, polyester imide, and polyphenylene sulfide.
A variety of reinforcing agents or fillers may be added to the
curable resins of this invention. Examples of reinforcing agents or
filler include glass cloths, such as cloth, roving cloth, chopped
mat, and surfacing mat; inorganic fibers, such as silica glass
cloth, carbon fiber cloth, asbestos, rockwool, and slag wool;
synthesis fiber cloths, such as aromatic polyamide cloth, textile
blends of glass fibers and aromatic polyamide fiber, acryl,
vinylon, polyester, polyamide, and polyimide; natural or
semi-synthesis fiber cloths or paper, such as cotton cloth, flax,
felt, craft paper, cotton paper, paper composed of pulp and glass
fibers, semicarbon fibers; chops of fibers constituting these
cloths or paper; and inorganic materials, such as glass bulb, glass
powder, silica, alumina, silica alumina, aluminum hydroxide,
asbestos, calcium carbonate, calcium silicate, graphitecarbon,
carbon black, caolin clay, baked caolin, mica, talk, aluminum,
copper, iron, iron oxides, synthesis mica, natural mica,
semiconductor, boron nitride, ceramics and the like.
Dye stuffs, pigments, thickners, lubricants, coupling agents,
flame-retardant, self-extinguishing agents, and the like may be
added to the curable resin.
The temperature for curing the curable resin composition depends on
the presence or the absence of a catalyst and the kind and the
proportion of components constituting the resin composition. In
general, the temperature may be in the range of
100.degree.-300.degree. C. It is preferable that the composition is
heated under pressure. The pressure may be in the range of from 0.1
to 500 Kg/cm.sup.2 and preferably from 50 to 150 Kg/cm.sup.2.
Laminate films or sheets and plates can be prepared from the resin
composition of the present invention. The resin composition can be
used as adhesives for metals, iron, aluminum, stainless steel,
nickel and copper; and plastic films or sheets, such as polyimide
film, polyester film, and the like. The resin compositions can be
used as heat-resistant adhesives.
The present invention is further illustrated by the following
non-limiting Examples and Control Runs.
All percentages and parts in these Examples and Control Runs are by
weight, unless otherwise specified.
EXAMPLE 1
2,2-Bis(4-cyanatophenyl)propane (750 parts) was prepolymerized at
160.degree. C. for 4 hours. Thermoplastic, saturated polyester
resin, which is either non-crystalline or of low crystallinity,
(Nippon Synthetic Chemical Industry Co., Ltd., Polyester LP 035)
having number average molecular weight of 16,000 calculated on the
basis of terminal functional group, and hydroxy value of 6 mg
KOH/gram (250 parts) and bisphenol A type epoxy resin (Oil Chemical
Shell Co., Ltd., Epikote 828) (50 parts) were added to the
prepolymer. Methyl ethyl ketone (MEK) was added to the mixture to
obtain a solution with resin content of 60%. The solution is called
Varnish (a).
Zinc octoate (catalyst) (0.12 parts) was added to Varnish (a). The
resulting solution was coated on silicone layer (150 .mu.m) coated
release paper, and dried to obtain an adhesive sheet with B-staged
resin layer 40 .mu.m thick.
Polyimide file (Du Pont; Kapton) 125 .mu.m thick was place on the
adhesive layer of the sheet and pressed with heat roll of
120.degree. C. The release paper was removed to transfer the
adhesive layer from the release paper to the polyimide film. Copper
foil 35 .mu.m thick was placed on the adhesive layer of the
polyimide film and pressed with stainless steel plate, and then
laminate-molded at 175.degree. C. and 30 Kg/cm.sup.2 for 2 hours to
obtain copper-clad film.
Physical and chemical tests of the film were effected. The results
are shown in Table 1.
EXAMPLE 2
1,4-Cyanatobenzene (450 parts) was prepolymerized at 160.degree. C.
for 4 hours. Thermoplastic, saturated polyester resin, which is
either non-crystalline or of low crystallinity (Nippon Synthetic
Chemical Industry Co., Ltd., Polyester LP 035) having number
average molecular weight of 16,000 calculated on the basis of
terminal functional group and hydroxy value of 6 mg KOH/gram (550
parts) and saturated polyester resin (Nippon Synthetic Chemical
Industry Co., Ltd., Polyester LP 044) having number average
molecular weight of 7,000 and hydroxy value of 15 mg KOH/g (100
parts) were added to the prepolymer. MEK was added to the mixture
to obtain a solution with resin content of 60%. The solution is
called Varnish (b).
Zinc octoate (catalyst) (0.07 parts) was added to Varnish (b). The
resulting solution was coated on silicone layer (150 .mu.m) coated
release paper, and dried to obtain an adhesive sheet with B-staged
resin layer 35-40 .mu.m thick.
Polyimide film (Du Pont; Kapton) 100 .mu.m thick was place on the
adhesive layer of the sheet and pressed with heat roll of
120.degree. C. The release paper was removed to transfer the
adhesive layer from the release paper to the polyimide film. Copper
foil 35 .mu.m thick was placed on the adhesive layer of the
polyimide film and pressed with stainless steel plate, and then
laminate-molded at 175.degree. C. and 30 Kg/cm.sup.2 for 2 hours to
obtain copper-clad film.
Physical and chemical tests of the film were effected. The results
are shown in Table 1.
COMPARATIVE RUN 1
The procedure of Example 1 was repeated except that only the
polyester resin of Example 1 was used as a resin component. The
results are shown in Table 1.
COMPARATIVE RUN 2
The procedure of Example 2 was repeated except that the polyester
resins were not used. The results are shown in Table 1.
EXAMPLES 3 AND 4
Varnish (a) and Varnish (b) of Examples 1 and 2 were stored at
30.degree. C. for 90 days. The test of storage stability was
effected. The results are shown in Table 2.
Copper foil-clad films were prepared in the same way as in Example
1 by using Varnish (a) and Varnish (b) after storing for 90 days.
The results are shown in Table 1.
EXAMPLE 5
2,2-Bis(4-cyanatophenyl)propane (675 parts) and
bis(4-maleimidephenyl)methane (75 parts) were prepolymerized at
160.degree. C. for 2 hours. Theremoplastic, saturated polyester
resin, which is either non-crystalline or of low crystallinity
(Nippon Synthetic Chemical Industry Co., Ltd., Polyester LP 035)
having number average molecular weight of 16,000 calculated on the
basis of terminal functional group, and hydroxy value of 6 mg
KOH/gram (250 parts) and bisphenol A type epoxy resin (Yuka Shell
Epoxy Co., Ltd., Epikote 828) (50 parts) were added to the
prepolymer. MEK was added to the mixture to obtain a solution with
resin content of 60%. The solution is called Varnish (c).
Zinc octoate (catalyst) (0.12 parts) was added to Varnish (a).
Varnish (a) was coated on silicone layer (150 .mu.m) coated release
paper, and dried to obtain an adhesive sheet with B-staged resin
layer 40 .mu.m thick.
Polyimide film (Du Pont; Kapton) 125 .mu.m thick was place on the
adhesive layer of the sheet and pressed with heat roll of
120.degree. C. The release paper was removed to transfer the
adhesive layer from the release paper to the polyimide film. Copper
foil 35 .mu.m thick was placed on the adhesive layer of the
polyimide film and pressed with stainless steel plate, and then
laminate-molded at 175.degree. C. and 30 Kg/cm.sup.2 to obtain
copper-clad film.
Physical and chemical tests of the film were effected. The results
are shown in Table 2.
EXAMPLE 6
1,4-Cyanatobenzene (382 parts) and bis(4-maleimidephenyl)ether (68
parts) were prepolymerized at 160.degree. C. for 1.5 hours.
Thermoplastic, saturated polyester resin, which is either
non-crystalline or of low crystallinity (Nippon Synthetic Chemical
Industry Co., Ltd., Polyester LP 035) having number average
molecular weight of 16,000 calculated on the basis of terminal
functional group and hydroxy value or 6 mg KOH/gram (550 parts) and
saturated polyester resin (Nippon Synthetic Chemical Industry Co.,
Ltd., Polyester LP 044) having number average molecular weight of
7,000 and hydroxy value of 15 mg KOH/g (100 parts) were added to
the prepolymer. MEK was added to the mixture to obtain a solution
with resin content of 60%. The solution is called Varnish (d).
Zinc octoate (catalyst) (0.07 parts) was added to Varnish (d). The
resulting solution was coated on silicone layer (150 .mu.m) coated
release paper, and dried to obtain an adhesive sheet with B-staged
resin layer 35-40 .mu.m thick.
Polyimide film (Du Pont; Kapton) 100 .mu.m thick was place on the
adhesive layer of the sheet and pressed with heat roll of
120.degree. C. The release paper was removed to transfer the
adhesive layer from the release paper to the polyimide film. Copper
foil 35 .mu.m thick was placed on the adhesive layer of the
polyimide film and pressed with stainless steel plate, and then
laminate-molded at 175.degree. C. and 30 Kg/cm.sup.2 for 2 hours to
obtain copper-clad film.
Physical and chemical tests of the film were effected. The results
are shown in Table 1.
COMPARATIVE RUN 3
The procedure of Example 5 was repeated except that only the
polyester resin of Example 5 was used as a resin component. The
results are shown in Table 1.
COMPARATIVE RUN 4
The procedure of Example 6 was repeated except that the polyester
resins were not used. The results are shown in Table 1.
EXAMPLES 7 AND 8
Varnish (c) and Varnish (d) of Examples 5 and 6 were stored at
30.degree. C. for 90 days. The test of storage stability was
effected. The results are shown in Table 2.
Copper foil-clad films were prepared in the same way as in Example
5 by using Varnish (a) and Varnish (b) after storing for 90 days.
The results are shown in Table 1.
TABLE 1
__________________________________________________________________________
Example or Comp. Comp. Comp. Comp. Comparative Run Ex. 1 Ex. 2 Ex.
3 Ex. 4 Ex. 1 Ex. 2 Ex. 5 Ex. 6 Ex. 7 Ex. 8 Ex. 3 Ex. 4
__________________________________________________________________________
Peel strength 25.degree. C. 2.4 2.7 2.4 2.7 2.2 1.1 2.3 2.7 2.3 2.7
2.2 1.0 of copper 150.degree. C. 1.7 1.3 1.8 1.3 0 0.1 1.8 1.5 1.9
1.6 0 0.2 foil 180.degree. C. -- 0.6 -- 0.5 0 -- -- 0.7 -- 0.8 0 --
Kg/cm 200.degree. C. 0.9 -- 0.9 -- -- 0* 1.0 -- 1.0 -- -- 0* Solder
resistance o o o o x x o o o o x x Flexing o o o o o x o o o o o x
characteristics solvent TCE o o o o .DELTA. o o o o o .DELTA. o
resistance MEK o o o o x o o o o o x o toluene o o o o x o o o o o
x o Surface resistance 1.4 0.65 2.0 0.40 0.03 5.0 1.1 0.7 1.7 0.52
0.03 4.0 (.OMEGA. .times. 10.sup.12)
__________________________________________________________________________
Note:- Solder Resistance . . . The sample was floated on melt
solder at 260.degree. C. for 20 seconds. "o" . . . No damage; "x" .
. . Flexing characteristics . . . Copper foil was removed from the
sample by etching. Metal wire having diameter of 1 mm was wound
around the resin plate. Whether or not the plate was broken was
observed. "o" . . . no damage "x" . . . craze Solvent resistance .
. . The sample was immersed in each of 1,1,1trichloroethane, MEK
and toluene. Appearance was observed. "o" . . . no damage,
".DELTA." . . . slight change "x" . . . great Surface resistance .
. . According to JIS C 6481 C - 90/20/65 + C - 96/40/90 treatment
*means that copper foil was peeled from the polyimide film.
TABLE 2 ______________________________________ Varnish (a) Varnish
(b) Varnish (c) Varnish (d) of Ex. 3 of Ex. 4 of Ex. 7 of Ex. 8
Viscosity (CPS) at 30.degree. C.
______________________________________ Storage 0 15,300 23,000
16,600 24,300 time 10 15,400 23,200 16,700 24,300 (day) 20 15,600
23,300 16,700 24,500 30 15,900 23,300 16,700 24,500 60 16,500
23,500 16,900 24,700 90 16,800 24,000 17,100 24,800
______________________________________
The following components were used in the following Examples and
Comparative run:
Thermosetting Resin A . . . Prepolymer obtained by heating
2,2-bis(4-cyanatophenyl)propane at 160.degree. C. for 3 hrs.
Thermosetting Resin B . . . Prepolymer obtained by heating
2,2-bis(4-cyanatophenyl)propane and bis(4-maleimidophenyl)methane
(638:113) at 160.degree. C. for 1.5 hrs.
Polyester Resin C . . . Nippon Synthetic Chemical Industry Co.,
Ltd.; Polyester LP-035 having number average molecular weight of
16,000 hydroxy value of 6 mg KOH/g
Polyester Resin D . . . Nippon Synthetic Chemical Industry Co.,
Ltd.; Polyester LP-011 having number average molecular weight of
16,000, hydroxy value of 6 mg KOH/g and density of 1.21
Polyester Resin E . . . Nippon Synthetic Chemical Industry Co.,
Ltd.; Polyester SP-170 having number average molecular weight of
19,000, hydroxy value of 5 mg KOH/g and density of 1.32
Polyepoxy Resin F . . . Yuka Shell Epoxy Co., Ltd.; Epikote 828
Thermoplastic Resin G . . . Acrylonitrile-butadiene copolymer
Thermoplastic Resin H . . . Thermoplastic polyurethane
EXAMPLE 9
Component A (70 parts) and component C (30 parts) were mixed. Mixed
solvent of MEK and toluene (1:1) was added to the mixture to obtain
varnish with resin content of 60%.
Iron acetylacetonate (0.01 part) was added to the varnish. The
resulting solution was coated on two aluminum plates 2.5 mm thick,
and dried. The two plates piled up to face the coated surfaces
thereof, and were fastened by clip, and then heated at 170.degree.
C. for 1 hr. to cure the resin component. Adhesive strength under
shear of the resulting plate was measured. The results are shown in
Table 3.
EXAMPLES 10-20 AND COMPARATIVE RUN 9-12
The procedures of Example 9 were repeated by using components given
in Table 3. The result are shown in Table 3.
TABLE 3 ______________________________________ Adhesive strength
under shear Ex. or Component Kg/cm.sup.2 Comp. Ex. A B C D E F G H
25.degree. C. 150.degree. C. ______________________________________
Ex. 9 70 30 250 125 Ex. 10 70 30 218 102 Ex. 11 70 30 201 93 Comp.
9 70 30 165 70 Comp. 10 70 30 180 83 Ex. 12 70 25 310 246 Ex. 13 70
25 250 212 Ex. 14 70 25 227 194 Ex. 15 70 30 240 120 Ex. 16 70 30
220 100 Ex. 17 70 30 200 95 Comp. 11 70 30 160 70 Comp. 12 70 30
180 85 Ex. 18 70 25 305 240 Ex. 19 70 25 250 210 Ex. 20 70 25 230
200 ______________________________________
EXAMPLE 21
2,2-Bis(4-cyanatophenyl)propane (200 parts) and Polyepoxy Resin F
(5 parts) were prepolymerized at 150.degree. C. for 3 hours.
Polyester Resin C (140 parts) and maleic acid-addition
1,2-polybutadiene in which maleic anhydride is bonded to C-C double
bond (Nippon Soda Co., Ltd.; BN-1010) having molecular weight of
1,000 and acid value of 110 (5 parts) were mixed with the
prepolymer. MEK was added to the mixture to obtain resin solution
with resin level of 40%. Finely divided silica (Nippon Aerogil Co.,
Ltd.; R-202) (4 parts) was added to the solution to form varnish
(l).
Zinc octoate (0.16 parts) and 1,1-bis(tertiary-butylperoxy)
3,3,5-trimethylcyclohexane (0.3 parts) were added to varnish (e).
The resulting solution was coated on polyimide film, and dried at
120.degree. C. for 5 minutes. Copper foil 35 .mu.m thick was placed
on the adhesive surface of the film, and press-molded at
170.degree. C. for 50 minutes at 20 Kg/cm.sup.2 to obtain copper
foil-clad film. The physical and chemical tests of the film were
effected. The results are shown in Table 4.
EXAMPLE 22
2,2-Bis(4-cyanatophenyl)propane (190 parts),
bis(4-maleimidophenyl)methane (10 part) and Polyepoxy Resin F (4
parts) were prepolymerized at 150.degree. C. for 3 hrs.
Polyester Resin C was added to the prepolymer. MEK was added to the
mixture to obtain varnish (f) with resin content of 40%.
Copper-clad film was prepared in the same way as in Example 21 by
using varnish (f). The results are shown in Table 4.
EXAMPLE 23
The prepolymer of Example 22, Polyester Resin C and the maleic
acid-addition 1,2-polybutadiene of Example 21 were used as in
Example 21 to obtain varnish (h).
Copper-clad film was prepared in the same way as in Example 21 by
using varnish (h). The results are shown in Table 4.
TABLE 4 ______________________________________ Ex. 21 Ex. 22 Ex. 23
______________________________________ Peel strength 25.degree. C.
2.5 2.3 2.4 of copper foil 150.degree. C. 1.5 1.5 1.4 Kg/cm)
200.degree. C. 0.5 0.6 0.5 Solder resistance o o o Flexing
characteristics o o o Solvent TCE o o o resistance MEK o o o
Toluene o o o Surface resistance 1.0 1.0 1.0 (.OMEGA. .times.
10.sup.12) ______________________________________
* * * * *